Molecular complexes for use as electrolyte components

ABSTRACT

An molecular complex is provided which includes a linear polymer associated with a cyclic molecule to form a rotaxane of the general formula, ##STR1## where R 1  and R 2  are blocking end groups of size and character sufficient to prevent dethreading of the rotaxane and said R 1  and R 2  the same or different; 
     where the cyclic molecule comprises a cyclic skeleton and at least one A functional group, said functional group attached to the cyclic skeleton; 
     where A is selected from the group consisting of polymerizable functional groups, cation complexing groups, anion complexing groups and ionic species; and 
     wherein at least one of R 1 , R 2  and A are selected from the group consisting of cation complexing groups, anion complexing groups and ionic species. 
     The molecular complex may used in an electrolyte.

This invention relates to electrolytes and/or electrolyte additives forelectrolytic cells and electrochemical devices, such as batteries,capacitors, fuel cells and displays, prepared therefrom.

BACKGROUND OF THE INVENTION

The electrochemical art desires to improve the operating characteristicsof electrolytes used in electrochemical devices. In devices such asbatteries, capacitors and displays, these electrolytes additionally mustbe highly conductive in order to allow useful current flux during use.In addition, the electrolyte must be chemically and electrochemicallystable towards both cathode and anode materials.

When a potential is applied across an electrolytic cell containing aconventional electrolyte, the cations and anions migrate to the negativeand positive electrodes, respectively, thereby forming a charge gradientin the electrolyte. This effect is particularly pronounced in solidpolymer electrolyte (SPE) materials which, due to the rigidmacromolecular structure of the electrolyte, has considerably reducedcationic mobility and reduced overall ionic mobility. Attempts have beenmade to prepare a solid polymer electrolyte in which only one of thecharged species has mobility by fixing the anions to the polymeric chainso that only the cations are mobile. While immobilizing the anion on thepolymer electrolyte chain has the effect of preventing migration duringuse, it has the additional undesirable effect of reducing cationmobility (and hence conductivity) because of the high affinity of thecation to the immobilized anion. Thus, it is desirable to improve theoperating characteristics of electrolytes and to overcome these andother operational limitations inherent in electrochemical devices. Oneway of overcoming the limitations of the materials currently used in theelectrochemical art is to develop and investigate new materials fortheir potential application in electrochemical cells.

Interlocking molecular systems which self-assemble have been the objectof much recent interest and investigation; however, they have not beenexamined for use in electrochemical cells. Interlocking molecularsystems include rotaxane complexes formed by noncovalent interactionsbetween a linear molecule and a cyclic molecule which results in the"threading" of the cyclic molecule or "bead" onto the linear molecule"string". Sterically large terminal groups on the linear molecularstring prevent the decomplexation or "de-threading" of the cyclicmolecular "beads". Recently, the synthesis and characterization ofself-assembling "rotaxanes" have been reported. The interested reader isdirected to Stoddart ("Making Molecules to Order" Chemistry in Britain,714-718, August 1991), Stoddart ("Cyclodextrins, Off-the-ShelfComponents for the Construction of Mechanically Interlocked MolecularSystems" Angew. Chem. Int. Ed. Eng. 31(7), 846-8, 1992), Rao et al.("Self-Assembly of a Threaded Molecular Loop" J. Am. Chem. Soc. 112,3614-5, 1990) and Harada et al. ("Preparation and Characterization ofPolyrotaxanes Containing Many Threaded Cyclorotaxanes" J. Org. Chem. 58,7524-8, 1993) for further information.

Many rotaxane complexes function as "molecular shuttles" by moving backand forth between identical stations along the length of the linearpolymer or molecule. Research directed by Stoddart has succeeded inproducing a rotaxane complex including a cyclic molecule (made up of twobipyridinium units and two bridging p-xylyl spacers) which moves backand forth between aromatic sites on a linear polyether string (See,"Molecular Shuttle: Prototype for molecular machine" C&EN, 4-5 (Jul. 1,1991)). The shuttle may be activated by chemical and electrochemicaltriggers (See, "A Chemically and Electrochemically Switchable MolecularShuttle" Nature 369, 133-7 (May. 12, 1994)); however, a practicalapplication for such molecules has yet to be proposed.

While these interlocking molecular systems have generated muchexcitement in the scientific community because of their ability toself-assemble and self-replicate at a molecular level, practicalapplications utilizing these self-assembling complexes have not beenrapidly forthcoming.

It is the object of the present invention to provide a molecular complexwhich can be used in an electrolyte. It is a further object of theinvention to provide a molecular complex which exhibits improvedconductivity and ion transport. It is a further object of the presentinvention to provide an electrolyte exhibiting improved conductivity andion transport. It is yet a further object of the present invention toprovide a precursor which improves the control of the nature of theinterface between the electrode surface and the solution. It is yet afurther object of the present invention to utilize rotaxane complexes inelectrochemical and electrolytic devices.

SUMMARY OF THE INVENTION

The present invention overcomes the above-stated of the electrolytes ofthe electrochemical art by the use of novel molecular complexes inelectrolyte compositions. In one aspect of the invention, an electrolytecomposition includes a linear polymer associated with a cyclic moleculeto form a rotaxane of the general formula, ##STR2## where R₁ and R₂ areblocking end groups of size and character sufficient to preventdethreading of the rotaxane and which are the same or different;

where the cyclic molecule comprises a cyclic skeleton and at least one Afunctional group, said functional group attached to the cyclic skeleton;and

where A is selected from the group consisting of polymerizablefunctional groups, cation complexing groups, anion complexing groups andionic species.; and wherein at least one of R₁, R₂ and A are selectedfrom the group consisting of cation complexing groups, anion complexinggroups and ionic species.

By "blocking end groups", as that term is used herein, it is meant toinclude terminal substituents on the linear molecule which are of a sizeand a character sufficient to prevent dethreading of the rotaxane.Dethreading of the rotaxane occurs when the cyclic molecule decomplexesfrom the linear molecule. The blocking end groups may be of a stericsize which prevents the cyclic molecule from moving past the blockingend group and, thereby, dethreading. Alternatively, the blocking endgroup may be of a character which discourages the approach of the cyclicend group to the blocking end group and thereby prevents dethreading,for example, when there exists a repulsive interaction between theblocking end groups and the cyclic molecule.

In preferred embodiments, at least one of R₁ and R₂ may be block andgraft copolymer blocking end groups. The blocking end groupsadditionally may be a polymerizable functionality, an ionicfunctionality, a cation complexing functionality or an anion complexingfunctionality. The blocking end group may be a blocking end groupsensitive to alignment in an electric field or to alignment based onhydrophobic-hydrophilic interactions. In other preferred embodiments,the A functional group may be attached to the cyclic skeleton of thecyclic molecule through a linear oligomer with one to 20 repeatingunits. At least two A functional groups may be attached to the cyclicskeleton of the cyclic molecule. The two or more A functional groups maybe the same or different. In another preferred embodiment, the molecularcomplex may include a plurality of cyclic molecules on a single linearmolecule.

In yet another preferred embodiment, R₁ and R₂ are blocking end groupsselected from the group consisting of cation complexing groups, anioncomplexing groups and ionic species and A includes a polymerizablefunctional group. A polymerized molecular complex may be obtained byreacting at A to link adjacent cyclic molecules.

In yet another preferred embodiment, R₁ and R₂ are polymerizableblocking end groups and A is a cation complexing group, anion complexinggroup and ionic species. A polymerized molecular complex may be obtainedby reacting at R₁ and R₂ to link adjacent linear molecules.

In another aspect of the present invention, a method of transporting anion within an electrolyte composition including a molecular complexcomprising a linear molecule associated with a cyclic molecule isprovided. The cyclic molecule includes a functional group attachedthereto, which is capable of interacting with an ion. The cyclicmolecule is located between a pair of blocking groups of the linearmolecule and is capable of motion along the length of the linearmolecule between the blocking groups. An ion is introduced into theelectrolyte composition and a voltage is applied across the electrolytecomposition. The ion migrates, whereby the functional group interactingwith the ion moves along the length of the linear molecule in the samedirection as the ion and transfers the ion to a functional group of anadjacent cyclic molecule.

In yet another aspect of the invention, a method of transporting an ionwithin an electrolyte composition including a molecular complexcomprising a linear molecule associated with a cyclic molecule isprovided, in which the cyclic molecule having limited mobility in theelectrolyte composition. The cyclic molecule is located between a pairof blocking groups of the linear molecule, and the blocking groups arecapable of interacting with an ion. The linear molecule is capable ofmotion along the length of the linear molecule between the blockinggroups. An ion is introduced into the electrolyte composition and avoltage is applied across the electrolyte composition. The ion migrates,whereby the functional group interacting with the ion moves along thelength of the linear molecule in the same direction as the ion andtransfers the ion to a functional group of an adjacent linear molecule.

The molecular complex of the present invention provides an electrolytecomponent of high conductivity and ion mobility.

BRIEF DESCRIPTION OF THE DRAWING

The novel features of the invention both as to its structure andoperation is best understood from the accompanying drawings, taken inconjunction with the accompanying description, in which similarreference characters refer to similar elements, and in which:

FIG. 1 illustrates an embodiment of the molecular complex of the presentinvention;

FIG. 2 illustrates an embodiment of the molecular complex of the presentinvention showing linkage at the linear molecule;

FIG. 3 illustrates (a) alignment substantially along the axis of thelinear molecule; and (c) stacking alignment of the molecular complexesof the present invention;

FIG. 4 is a schematic illustration of ion transport by the electrolyteof the present invention; and

FIG. 5 illustrates an embodiment of the molecular complex of the presentinvention showing linkage of cyclic molecules.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention provides a novel molecular complex for use in anelectrolyte for electrolytic cells and electrochemical devices. Themolecular complex includes a linear molecule associated with a cyclicmolecule to form a rotaxane. The rotaxanes of the present invention arefunctionalized to impart properties required of an electrolytic cell,such as high ionic conductivity, high transport number, electrochemicalstability and reduced crystallinity. A novel aspect of the presentinvention is the introduction of a ion complexing or ionic group ontothe molecular complex, which is capable of interacting with ions in theelectrolyte.

The molecular complex of the present invention has the general formula,##STR3## where R₁ and R₂ are blocking end groups of size and charactersufficient to prevent dethreading of the rotaxane and which are the sameor different;

where the cyclic molecule comprises a cyclic skeleton and at least one Afunctional group, said functional group attached to the cyclic skeleton;and

where A is selected from the group consisting of polymerizablefunctional groups, cation complexing groups, anion complexing groups andionic species.

With reference to FIG. 1, a molecular complex 10 is shown including alinear molecule 12 having blocking end groups 13 and 14. Blocking endgroups 13 and 14 may be the same or different. A cyclic molecule 15 is"threaded" onto the linear molecule 12. The cyclic molecule 15 includesa cyclic skeleton 16, and at least one functional group 17 (A) which isattached to the cyclic skeleton. A novel aspect of the present inventionis that at least one of 17 (A), 13 (R₁) and 14 (R₂) is an ionic speciescapable of complexing or interacting with an ion.

If the linear molecule 12 is to interact favorably with the cyclicmolecule 15, the linear molecule should be of a size less than the sizeof the internal cavity of the cyclic molecule. The internal cavity sizemay differ greatly among various cyclic molecules. For example,cyclodextrins contain cylindrical cavities about 0.7 nm deep and 0.45nm, 0.7 nm and 0.75 nm for α-, β-and γ-cyclodextrin, respectively."Size" is determined by the space occupied by the group including anynormal configuration changes which the linear molecule undergoes insolution.

Since the linear molecule must be of considerable length, it istypically, but not necessarily, an oligomer or a polymer. The linearmolecule typically has a molecular weight (M_(w)) of greater than 200.Exemplary of suitable linear oligomers and polymers include, but are inno way limited to, polypropylene (PP), polyethylene (PE), polyester,polyethylene oxide (PEO), polypropylene oxide (PPO) andpolyethyleneimine (PEI). In molecular complexes of the presentinvention, oligomers and polymers of polyethylene oxide are particularlypreferred because such macromolecules have been used successfully inelectrolytic cells, can be easily manufactured to any desired length andcan form rotaxanes with a variety of cyclic molecules, most notablycyclodextrin.

The linear molecule 12 of the molecular complex 10 terminates withblocking end groups 13 and 14 of size and character sufficient toprevent dethreading of the rotaxane. A "sufficient" size is a functionof the size of the internal cavity of the cyclic molecule which is usedin the formation of the rotaxane. The blocking end group should be largeenough to prevent the cyclic molecule from "sliding" over the bulky endgroup and decomplexing the rotaxane. The blocking end group mayalternatively or additionally be of a character that preventsdecomplexation of the rotaxane. In particular, the blocking end groupmay interact repulsively with the cyclic molecule and thereby hinder itsapproach to the end group and the subsequent decomplexation of therotaxane. An example of a repulsive interaction is where both theblocking end group and the cyclic molecule are similarly charged. Theblocking end groups having sufficient character and size for the cyclicmolecules contemplated in this invention include by way of example, butare in no way limited to, 2-4-dinitrophenyl-, trialklysilyl-,trialklymethyl-, 4-tritylphenyl ether and triphenyl methyl-groups.

The blocking end group of sufficient size and character may be amacromolecule, derived from a block or graft copolymer. By"macromolecular graft or block", as that term is used herein, it ismeant a macromolecular subcomponent of block or graft copolymers. Graftor block copolymers contain long sequences of two or more differentmonomers. The macromolecular graft or block may be linear or branched,however, they must be of sufficient size or character to preventdethreading. The macromolecular graft or block is typically a block orgraft onto the linear molecule of the rotaxane which is itself anoligomer or a polymer. Use of block copolymers permit the assembly ofthe rotaxane along a portion of the polymer which is susceptible torotaxane formation (appropriate size and character, favorableinteractions between the linear cyclic molecules, etc), followed by theaddition of a bulky monomer to form a copolymer block which functions asthe blocking end group. Suitable graft and block macromolecules includebut are in no way limited to polyphosphazene, polydimethylsiloxane andpolypropylene oxide.

Bulky end groups may be selected to possess additional desirablefunctionalities. Bulky end groups may be a polymerizable functionality,an ionic functionality, a cation complexing functionality or an anioncomplexing functionality.

"Polymerizable functional groups" are capable of chain extensionreactions or cross-linking reactions to obtain structures of highermolecular weight. Conventional functional groups may include, by way ofexample and in no way limited to, p-isoprenylstyrene, substituteddivinylbenzene, isocyanate and imine derivatives. Polymerization can beaccomplished using any conventional method including photoinitiation,free radical polymerization, chemical initiation. It is contemplatedthat the molecular complex may be polymerized with a comonomer to form acopolymer or with itself to form a homopolymer. The comonomer may be anysmall organic molecule capable of reacting with the polymerizablefunctional group including, by way of example only, styrene, andacrylate and methacrylate derivatives.

The requirement that the bulky end group be of a size and character toprevent dethreading of the rotaxane may be met by the polymerizablefunctional group in the polymerized state, rather than in the unreactedstate. Since the blocking end group increases in size uponpolymerization, the actual functional group of the molecular complex maybe of insufficient size, which becomes sufficient upon polymerization.In one embodiment of the present invention, a series of rotaxanes 20includes a conventional blocking end group 22 and a rather smallpolymerizable blocking end group 24, i.e., a maleate. The maleic groupsthen can be polymerized to form a polyester backbone 26, thereby forminga network rotaxane 28. The polyester backbone 26 effectively serves asthe blocking end group. FIG. 2 illustrates this embodiment of thepresent invention.

"Cation complexing functionalities", "anion complexing functionalities"and "ionic functionalities" include charged and neutral species whichcan complex or interact with ions in the electrolyte. Cation complexingfunctionalities include, by way of example and in no way limited to,crown ethers, thio-crown ethers and AZA crowns. Anion complexingfunctionalities include, by way of example and in no way limited to,borates and organometallic species. Ionic functionalities include, byway of example and in no way limited to, sulfonates, phthlates,carboxylates and ammoniums. In molecular complexes of the presentinvention, which are capable of interacting with small alkaline earthand alkali metal cations, such as Li⁺, Na⁺ and proton (H+), areparticularly preferred. By "interaction", as contemplated by the presentinvention, that term is meant to include interactions that areelectrostatic, bases upon ion complexation interactions or chargeattraction.

The cyclic molecule 15 includes a cyclic skeleton 16 which can interactfavorably with the linear molecule 12 and is capable of bearing pendantA functional groups 17. In particular, it may be α-, β-, orγ-cyclodextrin; it may alternatively be a cyclic ether such as a crownether. The cyclic molecule further may include ring systems includingaromatic phenyl and pyridinium units, such ascyclobis(paraquat-p-phenylene). A novel aspect of the present inventionis the substitution of a functional end group A onto the cyclic skeletonof the cyclic molecule. A may be selected from the group consisting ofpolymerizable functional groups, ionic species, cation complexing groupsand anion complexing groups. The suitable chemical moieties for use as Aare similar to those used for R₁ and R₂ in that they are selected toperform the similar functions. "Polymerizable functional groups" arecapable of chain extension reactions or cross-linking reactions toobtain structures of higher molecular weight. "Cation complexinggroups", "anion complexing groups" and "ionic species" include chargedand neutral species which can complex or interact with oppositelycharged ions in the electrolyte. A functional end groups differ from theR₁ and R₂ blocking end groups in one important way. There is norequirement that A have a size or character sufficient to preventdethreading of the rotaxane, since A or the oligomeric pendant groupswhich may attach A to the cyclic skeleton do not serve to formrotaxanes. Rather, the functional group A is selected to have thedesired functional properties without regard to size.

The functional end group A optionally may be attached to the cyclicskeleton through a linear oligomer 11 comprised of between one to twentyrepeating units. Suitable oligomers include, but are in no way limitedto, polypropylene, polyethylene, polyester, polyethylene andpolypropylene oxide, polyphosphazene and polysiloxane.

There is at least one A functional end group attached to the cyclicskeleton of the cyclic molecule. In one embodiment of the presentinvention, there may be two or more A functional end groups, which maybe the same or different, attached to the cyclic molecule. The upperlimit to the number of A groups attached to the cyclic skeleton is basedon the number of reactive sites originally on the cyclic molecule whichcan be substituted for the functional end groups A of the presentinvention. For example, α-cyclodextrin, which is made up of six glucosemolecules and contains three active hydroxyl groups per glucosemolecule, has 18 potential sites on its cyclic skeleton for potentialsubstitution of the functional groups A of the present invention.Several of the active sites however, may be sterically inaccessible andthe number of sites that can be practically substituted is considerablyless. Further, the number of sites that it is desirable to substitute inorder to impart desirable properties to the electrolyte composition maybe considerably less and is preferably in the range of one to six.

It is within the scope of the present invention to thread a plurality ofcyclic molecules onto the linear molecule. The actual number of cyclicmolecules is limited by the number of available sites along the lengthof the linear molecule for interaction of the cyclic molecule. Harada etal. (J. Org. Chem. 58, 7524-28 (1993)) have reported threading as manyas 20 α-cyclodextrins on a polyethylene glycol chain of averagemolecular weight of 2000. The optimal number of cyclic molecules perrotaxane is that which best facilitates ion transport with theelectrolyte. One of ordinary skill can determine the optimum number ofcyclic molecules per rotaxane by measuring the transport number of themolecular complex. Appropriate measurements to determine transportnumber which are common to the electrochemical art will be readilyapparent and known to those art-skilled practitioners, for example, byuse of Hitthors Method.

It is further within the scope of the invention to substitute the cyclicmolecule with additional groups which do not immediately serve in iontransport or polymerization. The purpose of such additional groups onthe cyclic molecule may serve a variety of purposes, including, but notlimited to, to deactivate electrochemically unstable species which mayreact with other components of the electrolyte or to serve as aplasticizer in the electrolyte reducing crystallinity and promotingconductivity of the electrolyte. For example, chemical moieties withoutactive hydrogen are particularly desirable when the electrolyte isintended for use in a non-aqueous electrolyte-based system.Cyclodextrin, which contains reactive hydroxyl groups, preferably isreacted to inactivate those sites, for example, by reaction with analcohol to form an alkyl ether.

Within the electrolyte, the molecular complex may be aligned, either"end-to-end" so that blocking end groups from neighboring molecularcomplexes approach one another (see, FIG. 3(a)) or "stacked" so thateach molecular complex substantially is aligned with a neighboringmolecular complex and the respective functional groups A of the cyclicmolecule are in closest contact (see, FIG. 3(b)). It is possible thatboth alignments may exist in the electrolyte. It is recognized that themolecular complexes of the present invention may be fairly large andthat the actual configuration of the molecular complex in solution maybe more complex than that shown in FIG. 3. "Alignment", as that term isused herein, is meant to indicate a higher degree of order in aparticular direction as compared with a random orientation.

With reference to FIG. 3(a), molecular complexes 30 are shown. In thisparticular embodiment, blocking end group 13 may be a group which isdifferent from the blocking end group 14. In this manner, the molecularcomplex is aligned end-to-end. Such alignment may be promoted byappropriate selection of blocking end groups. For example, the blockingend groups may be charged ionic functional groups which are sensitive toalignment in an electric field. Alternatively, R₁ blocking end groups 13may be substantially hydrophobic (a hydrophobic head), while R₂ blockingend groups 14 may be polar or charged (a polar tail). The R₁ end groups13 will interact preferably and the R₂ end groups 14 will interactpreferably, resulting in the head-to-head and tail-to-tail alignmentobserved with surfactants. Molecular complexes may be stacked by similarselection of A and A* functional end groups, as shown in FIG. 3(b),where A and A* may be the same or different.

An electrolyte containing the molecular complex of the present inventionmay exhibit high ionic conductivity and is capable of promoting iontransport within the electrolyte without significant formation of anionic gradient. Lithium cation, Li⁺, is a preferred ion. The advantagesof the electrolyte composition in promoting ionic transport areillustrated with reference to FIG. 4. Molecular complexes 40 and 41 eachinclude a functional end group A which is a negatively charged species,here designated as A⁻. A positively charged cation M⁺ is associated withA⁻. The linear molecule 12 includes sites along its length whichinteract with the cyclic molecule 15 and the cyclic molecule 12 iscapable of motion along the length of linear molecule 12 in thedirections indicated by arrows 43 and 44. In the present embodiment, theion complexing or interacting group is the group A of the cyclicmolecule.

In operation, the electrolyte including the molecular complexes 40 and41 shown in FIG. 4(a) is disposed between a cathode and an anode (notshown) to form an electrolytic cell and a voltage is applied forcingionic flux across the cell. Suitable voltage is obtained by dischargingthe cell, using the electrochemical potential of the cell to induceionic flux, or by applying a potential across the cell. The free cationM⁺ migrates in the direction of the oppositely charged electrode (thecathode). The pendant group A⁻ is strongly associated with M⁺ and isdrawn with M⁺ towards the cathode along the length of the linearmolecule 12, which is assumed for the purposes of this explanation to bein the direction indicated by arrow 44. Further movement of the cyclicmolecule 15 on linear molecule 12 is prevented by the blocking end group13. However, the proximity of M⁺ to molecular complex 41 attracts thecyclic molecule 15 on molecular complex 21 to migrate in the directionindicated by arrow 43 and to approach M⁺. M⁺ then moves from its site onmolecular complex 40 to 41 and proceeds to move in the directionindicated by arrow 44 in the direction of the cathode (see, FIG. 4(c)).In this way, M⁺ is transported within the electrolyte from one molecularcomplex to a neighboring molecular complex. Because M+ is passed fromone anionic species to the next, no charge gradient develops in theelectrolyte. Further, because the functional end group A on the cyclicmolecule of the molecular complex is inherently capable of a wide degreeof movement (i.e., axial and radial motion), it is capable of travelingwith the free ion for short distances and thereby overcoming thedisadvantages of immobilized ions which have high affinity for the freeion. Freedom of movement may be even further enhanced by use of a linearoligomer to attach the A functional end group onto the cyclic skeleton.

In yet another embodiment of the molecular complex of the presentinvention, the molecular complex includes at least two polymerizablefunctional end groups. A plurality of such individual molecularcomplexes are polymerized through these polymerizable functional endgroups to form a polymerized molecular complex, as depicted in FIG. 5.In this embodiment, blocking end groups 13 and 14 are cation complexing,anion complexing or ionic blocking end groups which are capable ofassociating with an ion, here designated as M. The polymerized cyclicmolecules serve to anchor the network molecular complex, while thelinear molecule is able to shuttle back and forth. The linear moleculehas only limited mobility, however, as it can only shuttle back andforth between its respective blocking end groups. As discussed above,these network molecular complexes can effectively transport ions throughthe electrolyte, using the same shuttling motion as described for FIG.4(a)-(c). As the blocking end group 13 approaches a neighboring blockingend group, the ion associated with it can transfer to the neighbor andso on through the electrolyte.

In both of the embodiments presented above, the counterion is anchoredby the molecular complex. Its mobility is restricted, but not completelyeliminated. This provides versatility to the electrolyte, which canpermit some short range migration of the counterion with the mobile ionspecies, but not to the extent that an undesirable ionic charge gradientdevelops in the electrolyte. Therefore, the electrolyte will exhibitsuperior ion transport capabilities.

An electrolyte using the molecular complex of the present invention mayadditionally include conventional component used in electrolytes. Forexample, the electrolyte may additionally include solvents, plasticizersand electrolyte salts.

"Solvents" as used herein include compounds capable of solubilizingeither or both the molecular complex and the ion to be transported. Insome cases, addition of a solvent will result in a liquid electrolytewhere the molecular complex is completely solubilized or a gelelectrolyte, where the solvent interacts, but does not completelysolubilize the complex. "Plasticizers" as that term is used hereinincludes a non-reactive compound which reduces the crystallinity of theelectrolyte. Suitable plasticizers include, but are in no way limitedto, trialkylsilanes, alkanes, phosphate esters, phosphinate esters, andsaturated organic esters. These plasticizers may also be used aselectrolyte solvents. By "electrolyte salts," as that term is usedherein, it is meant a salt which is soluble in the electrolyte whichprovides the ion to be transported. Suitable electrolyte salts include,but are in no way limited to, salts of an alkoxide, an alkyl orhaloalkylcarboxylate or sulfonate.

EXAMPLES Example 1

Preparation of an ionically modified α-cyclodextrin:

This example shows the synthesis of a cyclic molecule (cyclodextrin), inwhich the functional group A is an ionic group, sodium sulfopropyl.

In a typical example, α-cyclodextrin (0.01 mole, 9.73 g. American MaizeProducts Co.) is dissolved in dimethyl sulfoxide (DMSO, 75 ml, AldrichChemical CO.), and the resulting solution dried over 4 Å molecularsieves (Davison Chemical Co.). The solution is transferred to a cleandry flask. 1,3-propane sulfone (1.34 g., 0.011 mole, Aldrich ChemicalCo.) is added to the α-cyclodextrin solution, and the flask's contentsare briefly mixed.

Sodium hydride (0.26 g, 0.011 mole, Aldrich Chemical Co.) and DMSO (20ml) are charged to a 250 ml three neck flask equipped with a stirrer,argon gas feed, thermometer, heating mantle, cylindrical pressureequalizing addition funnel and condenser. The α-cyclodextrin 1,3-propanesultone/DMSO solution is placed in the cylindrical funnel. This isslowly added to the stirred sodium hydride slurry. During the additionvigorous effervescence of hydrogen gas occurs from the reaction, and thetemperature of the flask's contents may rise above room temperature.After completion of the addition, the reactants are gently warmed withcontinuous stirring to about 55° to 70° C. for about 4 hr, and thenallowed to cool overnight to room temperature. Gentle heating during theday followed by cooling over night is repeated for the next 4 days. Thesolution is then filtered and DMSO removed at reduced pressure.

The product is identified as sodium sulfopropyl α-cyclodextrin.Confirmation of the product's identity is made by infrared spectroscopyand thin layer chromatography. The average degree of sulfonation is one;there is no favored site of sulfonation and all sites are expected to beequally substituted. It is expected that yield of sodium sulfopropylα-cyclodextrin will be in the range of 85%.

Example 2

Preparation of a rotaxane using a block copolymer:

This example shows the synthesis of a molecular complex including sodiumsulfopropyl α-cyclodextrin as the cyclic molecule, a linear moleculecontaining a poly(dimethyl siloxane) group as a first blocking end groupand methacrylate as a second blocking end group.

Protorotaxane formation: In a typical example, a poly(dimethylsiloxane)-poly (ethylene oxide) block copolymer (10.0 g, about 0.01mole, Huls America) is converted to the primary amine via treatment withPBr₃ and ammonia and dissolved in water (50 ml). The approximatecomposition of the copolymer is (CH₃)₃ SiO(CH₃)₂ Si(CH₂)₃ (OCH₂ CH₂)₁₈NH₂. The sodium sulfopropyl α-cyclodextrin of Example 1 (16.7 g, 0.015mole) is added to the aqueous solution, and the solution agitated byultrasonic energy. After agitation the solution is added dropwise toacetone (500 ml) with vigorous stirring to induce precipitation of theprotorotaxane. The precipitate is filtered and dried in vacuum at about75° C.

End-blocking with a polymerizable blocking group: Methacryloyl chloride(1.5 g, 0.015 mole) is dissolved in DMSO (25 ml). The solution is placedin a flask equipped with a nitrogen gas sparge and a magnetic stirrer.Dried protorotaxane (24 g) is added to the flask and allowed to reactwith methacryloyl chloride for 24 hours at ambient temperature. The acidchloride predominantly reacts at the primary amine. Solvent is removedunder reduced pressure. The product is identified as a molecular complexhaving a poly(ethylene oxide) linear molecule with apoly(dimethylsiloxane) blocking end group, a methacrylamide blocking endgroup, and a sodium sulfopropyl α-cyclodextrin cyclic molecule. Thestructure of the molecular complex product is confirmed by NMR.

Example 3

Polymerization of a molecular complex:

This example illustrates the polymerization of a molecular complexthrough reaction at the blocking end groups of the linear molecule.

In a typical example, the molecular complex of Example 2 (25 g) isdissolved in water (150 ml). The solution is transferred to a 250 mlthree neck flask equipped with a stirrer, argon gas feed, thermometer,heating mantle and condenser. The solution warmed to 50° C. withstirring under argon gas. 2,2'-azobis(N,N'-dimethylencisobutyramidine)dihydrochloride (0.05 g, Wako Pure Chemical Industries, Ltd.) is thenadded to the flask, and the flask's contents is held at 50° C. for 8hours. During this time the apparent viscosity of the solution increasesto a syrup consistency due to as increase in molecular weight. Theproduct is identified as a polymerized molecular complex having apoly(ethylene oxide) linear molecule with a poly(dimethylsiloxane)blocking end group and a polymerized poly(methacrylamide end group and asodium sulfopropyl α-cyclodextrin cyclic molecule. Molecular weightdetermination is carried out by GPC. M_(N) of about 10,000-20,000 isexpected.

Example 4

Preparation of an α-cyclodextrin modified with polymerizable ionicgroups:

This example shows the synthesis of a cyclic molecule (cyclodextrin), inwhich the functional group A is both anionic and polymerizable.

In a typical example, α-cyclodextrin (0.05 mole, 48.7 g, American MaizeProducts Co.) is dissolved in DMSO (250 ml, Aldrich Chemical Co.). Thesolution is transferred to a clean dry 500 ml three neck flask equippedwith stirrer, heating mantle, thermometer, argon gas feed and condenser.Maleic anhydride (14.7 g, 0.015 mole, Aldrich Chemical Co.) and about0.2 g acid-treated Fuller's earth are added to the α-cyclodextrinsolution, and the flask's contents are briefly mixed. The contents ofthe flask are heated to 70° C. for several hours and then allowed tocool overnight to room temperature. The solution is then filtered andneutralized with lithium hydroxide (Aldrich Chemical Co.). DMSO andtrace water are removed at reduced pressure.

The product is identified as lithium maleated α-cyclodextrin.Confirmation is made by infrared spectroscopy and thin layerchromatography. The average degree of maleation is three; however,maleation is expected to occur equally at all available sites. Yield oflithium maleated α-cyclodextrin expected to be in the range of 99%.

Example 5

Preparation of a rotaxane using poly(ethylene oxide):

This example shows the synthesis of a molecular complex including thelithium maleated α-cyclodextrin of Example 4 as the cyclic molecule andpoly(ethylene oxide) as the linear molecule having phthalate as an ionicblocking end group.

Protorotaxane formation: Poly(ethylene oxide) (20.0 g, about 0.02 mole,Scientific Polymer Products) is dissolved in water (100 ml). The lithiummaleated α-cyclodextrin of Example 4 (32.3 g, 0.025 mole) is added tothe aqueous solution, and the solution is agitated by ultrasonic energy.After agitation the solution is added dropwise to acetone (500 ml) withvigorous stirring to induce precipitation of the protorotaxane. Theprecipitate is filtered and dried in vacuum at about 75° C.

End-blocking with an ionic blocking group: Phthalic anhydride (28.4 g,0.2 mole) is dissolved in DMSO (200 ml). The solution is placed in aflask equipped with a magnetic stirrer. Dried protorotaxane (45 g) isadded to the flask and allowed to react with the phthalic anhydride forseveral hours at 70° C. The solvent and most of the residual phthalicanhydride are removed under reduced pressure. Crude product is taken upin water, neutralized with lithium hydroxide, and washed several timeswith ethyl ether. The aqueous phase is then dried at 75° C. in an airoven and the solid residue at 75° C. in vacuum. The product isidentified as a molecular complex having a poly(ethylene oxide) linearmolecule with phthalic anhydride blocking end groups and a lithiummaleated α-cyclodextrin cyclic molecule. The structure of the molecularcomplex product is confirmed by NMR

Example 6

Polymerization of a molecular complex:

This example shows the polymerization of a molecular complex throughreaction at the functional group A of the cyclic molecule.

In a typical example, the molecular complex of Example 5 (25 g) isdissolved in propylene carbonate (25 ml). Styrene (5.0 g, 0.048 mole,Aldrich Chemical Co.) and t-butyl peroctoate (0.05 g, Lucidol) are addedto the solution and dissolved. About 0.5 g of the solution is sealed ina 0.001 in thick glass polymerization cell, and the cell placed in an80° C. circulating air oven for four hours. After cooling to roomtemperature, a gelled polymer film is removed from the casting cell. Theproduct is identified as a polymerized molecular complex having apoly(ethylene oxide) linear molecule with lithium phthalate esterblocking end groups and a copolymer gel comprised of styrene and lithiummaleated α-cyclodextrin. The gel swells but does not dissolve is DMSO.

Example 7

Preparation of an orienting rotaxane:

This example illustrates the formation of a molecular complex capable ofbeing aligned in a head-to-tail orientation.

Protorotaxane formation: In a typical example, α-cyclodextrin (19.5 g,0.02 mole) and triethyl amine (12.2 g, 0.12 mole, Aldrich Chemical Co.)are dissolved in DMSO (50 ml). Trimethylchlorosilane (13.0 g, 0.12 mole,Aldrich Chemical Co.) in DMSO (25 ml) is added to the stirredα-cyclodextrin solution, the solution warmed to about 55° C. for 6hours, and cooled overnight. Although silylation may occur at anyavailable hydroxyl group, the six primary hydroxyls of theα-cyclodextrin are silylated preferentially. Amine hydrochloride salt isremoved from the product solution by filtration, and solvent removedfrom the product under reduced pressure. The structure of thetrimethylsilyl modified α-cyclodextrin is confirmed by infraredspectroscopy. A poly(dimethylsiloxane)-poly(ethylene oxide) blockcopolymer (10.0 g, about 0.01 mole, Huls America) is dissolved in water(50 ml). The approximate composition of the copolymer is (CH₃)₃SiO(CH₃)₂ Si(CH₂)₃ (OCH₂ CH₂)₁₈ OH. Trimethylsilyl modifiedα-cyclodextrin is added to the aqueous solution, and the solutionagitated by ultrasonic energy at 30° C. for 60 minutes. After agitationthe solution is added dropwise to acetone (500 ml) with vigorousstirring to precipitate the protorotaxane. The precipitate is filteredand dried in vacuum at about 75° C.

End blocking of the rotaxane: Phthalic anhydride (89 g, 0.6 mole), DMSO(250 ml) and about 1 g acid-treated Fuller's earth are added to a cleandry 500 ml three neck flask equipped with stirrer, heating mantle,thermometer, argon gas feed and condenser. The α-cyclodextrin solutionand the flask's contents are briefly mixed. The protorotaxane is addedto the flask, and the flask's contents are heated to 70° C. for severalhours and then allowed to cool overnight to room temperature. Thesolution is then filtered and neutralized with lithium hydroxide(Aldrich Chemical Co.). DMSO and trace water are removed at reducedpressure.

The molecular complex of this example is structured identically to anionic surfactant with a hydrophobic tail (the silicone end) andhydrophilic head (the lithium phthalate ethoxylate). In a monolayer filmthis rotaxane will preferentially orient itself tail to tail and head tohead.

Example 8

Preparation of an Electrochemical Cell:

This example illustrates the formation of an electrolyte based on amolecular complex. The electrolyte is used in the fabrication of anelectrochemical cell.

Electrolyte precursor: An electrolyte precursor is formulated asfollows:

30% wt of the ionically modified molecular complex of Example 2

50% wt of a mixture (1:1) of ethylene carbonate and dimethyl carbonate

10% wt of polyethylene glycol diacrylate (comonomer)

9.9% wt of ethoxylated trimethyl propane triacrylate (comonomer)

0.1% of t-butyl peroctoate (thermal initiator)

The electrolyte precursor is prepared by mixing the components to form asolution.

The precursor is stored in a refrigerator until needed for coating.

Cathode precursor: A cathode precursor is formulated as follows:

85% wt of LiMn₂ O₄

8% wt of acetylene black

4% wt of graphite

3% wt of EPDM (thermoplastic elastomer binder) The cathode precursor isprepared by blending the components in a highly volatile hydrocarbonsolvent until a uniform consistency is achieved.

Anode material: An anode is prepared using a piece of lithium metal of50 μm in thickness.

Cell assembly: The electrochemical cell is prepared by first coating thesuspension of the cathode precursor on a metallic substrate (currentcollecter). The cathode precursor is heat treated to remove any residualtrace of solvent and water in order to obtain a dry thickness ofapproximately 50 μm, corresponding to approximately 1 mAh/cm² of cathodeactive material capacity. The electrolyte precursor is then overcoatedon the cathode. The thickness of the electrolyte layer is approximately25 μm. Some of the electrolyte precursor penetrates into the cathodelayer. This sub-assembly is exposed to heat (60° C. ) for a few minutesin order to initiate polymerization and crosslinking of the molecularcomplex and comonomers of the electrolyte precursor, thereby yielding asolid polymer electrolyte having intimate contact with the cathode. Thelithium metal anode is then laminated to the surface of the polymerelectrolyte resulting in an electrochemical cell. This cell will producean open circuit voltage of 3.8 volts corresponding to the thermodynamicpotential value of lithium versus manganese oxide.

Example 9

Preparation of an Ethoxylated Functionalized Cyclodextrin:

This example shows the synthesis of an ethoxylated functionalizedcyclodextrin, in which the functional group A is an ionic group (lithiumsuccinate ester) and A is linked to the cyclodextrin ring through anethylene oxide group.

In a typical example, hydroxyethyl α-cyclodextrin (0.1 mole, 123 g.American Maize Products Co.) is dissolved in DMSO (300 ml), and theresulting solution dried over 4Å molecular sieves. The solution istransferred to a clean dry flask. Succinic anhydride (30 g, 0.30 mole,Aldrich Chemical Co.) and about 0.2 g acid-treated Fuller's earth areadded to the α-cyclodextrin solution, and the flasks's contents arebriefly mixed. The contents of the flask are heated to 70° C. forseveral hours and then allowed to cool overnight to room temperature.The solution is then filtered and neutralized with lithium hydroxyide(Aldrich Chemical Co.). DMSO and trace water are removed at reducedpressure.

The product is identified as lithium succinoyl ethyl α-cyclodextrin.Confirmation is made by infrared spectroscopy and thin layerchromatography. The average degree of succination is three; however,succination is expected to occur equally at all available sites.

Other embodiments of the invention will be apparent to those skilled inthe art from a consideration of this specification or practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only, with the true scope and spiritof the invention being indicated by the following claims.

What is claimed is:
 1. A molecular complex, comprising:a linear polymerassociated with a cyclic molecule to form a rotaxane of the generalformula, ##STR4## where R₁ and R₂, are blocking end groups of size andcharacter sufficient to prevent dethreading of the rotaxane and said R₁,and R₂ are the same or different; where the cyclic molecule comprises acyclic skeleton and at least one A functional group, said functionalgroup attached to the cyclic skeleton; where A is selected from thegroup consisting of polymerizable functional groups, cation complexinggroups, anion complexing groups and ionic species; and wherein at leastone of R₁, R₂ and A are selected from the group consisting of cationcomplexing groups, anion complexing groups and ionic species; andwherein said A functional group is attached to the cyclic skeleton ofthe cyclic molecule through a linear oligomer with one to 20 repeatingunits.
 2. The molecular complex of claim 1, wherein at least two Afunctional groups are attached to the cyclic skeleton of said cyclicmolecule, said at least two A functional groups are the same ordifferent.
 3. The molecular complex of claim 1, wherein the molecularcomplex comprises a plurality of cyclic molecules associated with thelinear molecule.
 4. The molecular complex of claim 1, wherein at leastone of R₁ and R₂ are blocking end groups selected from the groupconsisting of block and graft copolymers.
 5. The molecular complex ofclaim 1, wherein at least one of R₁ and R₂ are blocking end groupsfurther selected from the group consisting of cation complexing groups,anion complexing groups and ionic species.
 6. The molecular complex ofclaim 1, wherein at least one of R₁ and R₂ is associated with additionalblocking end groups toward the continued formation of additionalmolecular complexes.
 7. A polymerized molecular complex, comprising:apolymer constituted from the molecular complex of claim 6, wherein thepolymerizable blocking end groups are reacted to form linked linearmolecules of adjacent molecular complexes.
 8. The polymerized molecularcomplex of claim 7, wherein the polymer is a copolymer including acomonomer.
 9. The molecular complex of claim 7 including an electrolytecomprising a plasticizer.
 10. The electrolyte of claim 9, furthercomprising a salt capable of interacting with the molecular complex. 11.The molecular complex of claim 7 including an electrolyte comprising asolvent capable of solubilizing the molecular complex.
 12. The molecularcomplex of claim 7 including an electrolyte comprising a solvent capableof solubilizing the molecular complex.
 13. The molecular complex ofclaim 1, wherein at least one of R₁ and ₂ are blocking end groupsselected from the group consisting of cation complexing groups, anioncomplexing groups and ionic species and A comprises a polymerizablefunctional group.
 14. A polymerized molecular complex, comprising:apolymer constituted from the molecular complex of claim 13, wherein theA polymerizable functional groups are reacted to form linked cyclicmolecules of adjacent molecular complexes.
 15. The polymerized molecularcomplex of claim 14, wherein the polymer is a copolymer including acomonomer.
 16. The molecular complex of claim 14 including anelectrolyte comprising a plasticizer.
 17. The electrolyte of claim 16,further comprising a salt capable of interacting with the molecularcomplex.
 18. The molecular complex of claim 14 including an electrolytecomprising a solvent capable of solubilizing the molecular complex. 19.The molecular complex of claim 14, including an electrolyte comprising asalt capable of interacting with the molecular complex.
 20. Themolecular complex of claim 1, wherein the functional group A is selectedfrom the group consisting of cation complexing groups, anion complexinggroups and ionic species.
 21. The molecular complex of claim 1, whereinsaid oligomer is selected from the group consisting of polyethyleneoxide, polypropylene oxide, polyester, polyphosphazene and polysiloxane.22. The composition of claim 1, wherein the cyclic molecule is selectedfrom the group consisting of cyclodextrins, crown ethers, crownthioethers, aza-crowns and cyclobis(paraquat-ρ-phenylene).
 23. Thecomposition of claim 1, wherein the linear polymer is selected from thegroup consisting of polyethylene oxide, polyester, polypropylene oxide,polyethylene, polypropylene, polysiloxane, polyphosphazene andpolyethyleneimine.
 24. The molecular complex of claim 1, wherein A isselected from the group consisting of cation complexing groups and ionicspecies capable of interacting with a cation, said cation selected fromthe group consisting of alkaline earth, alkali metal cations and proton.25. The molecular complex of claim 1, wherein A is selected from thegroup consisting of anion complexing groups and ionic species capable ofinteracting with an anion.
 26. The molecular complex of claim 1, whereinat least one of R₁ and R₂ is selected from the group consisting ofcation complexing groups and ionic species capable of selectivelyinteracting with a cation, said cation selected from the groupconsisting of alkaline earth and alkali metal cations and proton. 27.The molecular complex of claim 1, wherein at least one of R₁ and R₂ isselected from the group consisting of anion complexing groups and ionicspecies capable of selectively interacting with an anion.
 28. Themolecular complex of claim 1, wherein the blocking end group R₁ and R₂are selected such that the molecular complex is capable of alignment inan electric field.
 29. The molecular complex of claim 1, wherein theblocking end group R₁ and R₂ are selected such that the molecularcomplex is capable of alignment by hydrophobic-hydrophilic interactions.30. The molecular complex of claim 1 including an electrolyte comprisinga plasticizer.
 31. The electrolyte of claim 30, further comprising asolvent capable of solubilizing the molecular complex.
 32. The molecularcomplex of claim 1 including an electrolyte comprising a solvent capableof solubilizing the molecular complex.
 33. The molecular complex ofclaim 1 including an electrolyte comprising a salt capable ofinteracting with the molecular complex.
 34. The molecular complex ofclaim 1 including an electrolyte comprising a salt capable ofinteracting with the molecular complex.
 35. A molecular complex,comprising:a linear polymer associated with a cyclic molecule to form arotaxane of the general formula, ##STR5## where R₁ and R₂, are blockingend groups of size and character sufficient to prevent dethreading ofthe rotaxane and said R₁, and R₂ are the same or different; where thecyclic molecule comprises a cyclic skeleton and at least one Afunctional group, said functional group attached to the cyclic skeleton;where A is selected from the group consisting of polymerizablefunctional groups, cation complexing groups, anion complexing groups andionic species; and wherein at least one of R₁, R₂ and A are selectedfrom the group consisting of cation complexing groups, anion complexinggroups and ionic species; and wherein at least two A functional groupsare attached to the cyclic skeleton of said cyclic molecule, said atleast two A functional groups are the same or different.
 36. A molecularcomplex, comprising:a linear polymer associated with a cyclic moleculeto form a rotaxane of the general formula, ##STR6## where R₁ and R₂, areblocking end groups of size and character sufficient to preventdethreading of the rotaxane and said R₁, and R₂ are the same ordifferent; where the cyclic molecule comprises a cyclic skeleton and atleast one A functional group, said functional group attached to thecyclic skeleton; where A is selected from the group consisting ofpolymerizable functional groups, cation complexing groups, anioncomplexing groups and ionic species; and wherein at least one of R₁, R₂and A are selected from the group consisting of cation complexinggroups, anion complexing groups and ionic species; and wherein at leastone of R₁ and R₂ are blocking end groups further selected from the groupconsisting of cation complexing groups, anion complexing groups andionic species.
 37. A molecular complex, comprising:a linear polymerassociated with a cyclic molecule to form a rotaxane of the generalformula, ##STR7## where R₁ and R₂, are blocking end groups of size andcharacter sufficient to prevent dethreading of the rotaxane and said R₁,and R₂ are the same or different; where the cyclic molecule comprises acyclic skeleton and at least one A functional group, said functionalgroup attached to the cyclic skeleton; where A is selected from thegroup consisting of polymerizable functional groups, cation complexinggroups, anion complexing groups and ionic species; and wherein at leastone of R₁, R₂ and A are selected from the group consisting of cationcomplexing groups, anion complexing groups and ionic species; andwherein at least one of R₁ and R₂ is associated with additional blockingend groups toward the continued formation of additional molecularcomplexes.
 38. A polymerized molecular complex, comprising:a polymerconstituted from the molecular complex of claim 37, wherein thepolymerizable blocking end groups are reacted to form linked linearmolecules of adjacent molecular complexes.
 39. The polymerized molecularcomplex of claim 38, wherein the polymer is a copolymer including acomonomer.
 40. A molecular complex, comprising:a linear polymerassociated with a cyclic molecule to form a rotaxane of the generalformula, ##STR8## where R₁ and R₂, are blocking end groups of size andcharacter sufficient to prevent dethreading of the rotaxane and said R₁,and R₂ are the same or different; where the cyclic molecule comprises acyclic skeleton and at least one A functional group, said functionalgroup attached to the cyclic skeleton; where A is selected from thegroup consisting of polymerizable functional groups, cation complexinggroups, anion complexing groups and ionic species; and wherein at leastone of R₁, R₂ and A are selected from the group consisting of cationcomplexing groups, anion complexing groups and ionic species; andwherein at leas one of R₁ and R₂ are blocking end groups selected fromthe group consisting of cation complexing groups, anion complexinggroups and ionic species and A comprises a polymerizable functionalgroup.
 41. A polymerized molecular complex, comprising:a polymerconstituted from the molecular complex of claim 40, wherein the Apolymerizable functional groups are reacted to form linked cyclicmolecules of adjacent molecular complexes.
 42. The polymerized molecularcomplex of claim 41, wherein the polymer is a copolymer including acomonomer.
 43. A molecular complex, comprising:a linear polymerassociated with a cyclic molecule to form a rotaxane of the generalformula, ##STR9## where R₁ and R₂, are blocking end groups of size andcharacter sufficient to prevent dethreading of the rotaxane and said R₁,and R₂ are the same or different; where the cyclic molecule comprises acyclic skeleton and at least one A functional group, said functionalgroup attached to the cyclic skeleton; where A is selected from thegroup consisting of polymerizable functional groups, cation complexinggroups, anion complexing groups and ionic species; and wherein at leastone of R₁, R₂ and A are selected from the group consisting of cationcomplexing groups, anion complexing groups and ionic species; andwherein A is selected from the group consisting of cation complexinggroups and ionic species capable of interacting with a cation, saidcation selected from the group consisting of alkaline earth, alkalimetal cations and proton.
 44. A molecular complex, comprising:a linearpolymer associated with a cyclic molecule to form a rotaxane of thegeneral formula, ##STR10## where R₁ and R₂, are blocking end groups ofsize and character sufficient to prevent dethreading of the rotaxane andsaid R₁, and R₂ are the same or different; where the cyclic moleculecomprises a cyclic skeleton and at least one A functional group, saidfunctional group attached to the cyclic skeleton; where A is selectedfrom the group consisting of polymerizable functional groups, cationcomplexing groups, anion complexing groups and ionic species; andwherein at least one of R₁, R₂ and A are selected from the groupconsisting of cation complexing groups, anion complexing groups andionic species; and wherein at least one of R₁ and R₂ is selected fromthe group consisting of cation complexing groups and ionic speciescapable of selectively interacting with a cation, said cation selectedfrom the group consisting of alkaline earth and alkali metal cations andproton.
 45. A molecular complex, comprising:a linear polymer associatedwith a cyclic molecule to form a rotaxane of the general formula,##STR11## where R₁ and R₂, are blocking end groups of size and charactersufficient to prevent dethreading of the rotaxane and said R₁, and R₂are the same or different; where the cyclic molecule comprises a cyclicskeleton and at least one A functional group, said functional groupattached to the cyclic skeleton; where A is selected from the groupconsisting of polymerizable functional groups, cation complexing groups,anion complexing groups and ionic species; and wherein at least one ofR₁, R₂ and A are selected from the group consisting of cation complexinggroups, anion complexing groups and ionic species; and wherein at leastone of R₁ and R₂ is selected from the group consisting of anioncomplexing groups and ionic species capable of selectively interactingwith an anion.
 46. A molecular complex, comprising:a linear polymerassociated with a cyclic molecule to form a rotaxane of the generalformula, ##STR12## where R₁ and R₂, are blocking end groups of size andcharacter sufficient to prevent dethreading of the rotaxane and said R₁,and R₂ are the same or different; where the cyclic molecule comprises acyclic skeleton and at least one A functional group, said functionalgroup attached to the cyclic skeleton; where A is selected from thegroup consisting of polymerizable functional groups, cation complexinggroups, anion complexing groups and ionic species; and wherein at leastone of R₁, R₂ and A are selected from the group consisting of cationcomplexing groups, anion complexing groups and ionic species; andwherein the blocking end group R₁ and R₂ are selected such that themolecular complex is capable of alignment in an electric field.
 47. Amolecular complex, comprising:a linear polymer associated with a cyclicmolecule to form a rotaxane of the general formula, ##STR13## where R₁and R₂, are blocking end groups of size and character sufficient toprevent dethreading of the rotaxane and said R₁, and R₂ are the same ordifferent; where the cyclic molecule comprises a cyclic skeleton and atleast one A functional group, said functional group attached to thecyclic skeleton; where A is selected from the group consisting ofpolymerizable functional groups, cation complexing groups, anioncomplexing groups and ionic species; and wherein at least one of R₁, R₂and A are selected from the group consisting of cation complexinggroups, anion complexing groups and ionic species; and wherein theblocking end group R₁ and R₂ are selected such that the molecularcomplex is capable of alignment by hydrophobic-hydrophilic interactions.